Method of polymerizing nonwrin



Patented May 18, 1948 METHOD OF POLYMERIZING N ONWRIN- KLING OILS TO WRINKLING OILS Gordon-M. Williams, Glens Falls, N.'Y., assignor to New Wrinkle, Inc., Dayton, Ohio, is co poration of Delaware No Drawing. Application April 9, 1947, Serial N- 7!),478

, 1 This invention rel-ates to drying oils having the property of yielding wrinkle films when compounded with resins and driers to form a varnish and applied to a surface and dried.

This application is a division of my copending application, Serial Number 485,646, filed May 4, 1943, now Patent No. 2,431,357.

More particularly, the present invention relates to means whereby polymerization nuclei may be initially formed whereby to improve or increase the drying rate and wrinkle forming properties of drying oils by treatment according to the present invention. v

In the formation of surface wrinkles on a coating composition it is important that there be de- 5 Claims. (01. 260407) 2 sional polymerized nucleus. Linseed oil and other similar oils, n the other hand, form drawn out polymerized units which are comparatively loosely knit.

The present invention deals particularl with means whereby the initial formation of polymerizing nuclei may be established in drying oils VelOped a considerable degree of strain caused by v contraction or expansion, or both, between the surface layer and the body of the drying film. While the mechanism of drying of coating films is not clearly understood, it is believed to include polymerization (see Bennett's Driers and Bryin pa e 5, 1941, published by Chemical Publishing Company, Brooklyn, New York) Apparently, this contraction or expansion of the surface layer is a condition established by the initial formation of polymerized nuclei on the surface of the coating film to form a thin skin and the subsequent polymerization of the underlayers,

This

tends to set up the required strain and causes 7 the formation of the wrinkle texture or pattern. It is thus apparent that acceleration of the rate of formation of polymerized units, first on the surface layer and finally throughout the coating,

film, will aid materially in the speedy formation of the wrinkle texture or pattern which is desired. Furthermore, it is reasonable to assume that the more closely knit the polymerized associations are, the more uniform and pronounced will be the resulting wrinkle pattern or texture.

The exact manner in which the molecules of a drying oil orient themselves and interreact is not known. However, there is considerable evidence to indicate that polar bodies are first formed by the introduction of oxygen into the points of unsaturation. These polar molecules are then able to polymerize and form nuclei for further polymerization, and this gradualpolymerization of polar molecules leads ultimately to the hardening of the coating film.

Furthermore, it is understood that the difl'erence in drying characteristics between tung oil (China-wood oil) and other oils such as linseed oil is largely due to the fact that the former by virtue of its high degree of conjugation and symmetry is able to form a closely knit three dimenwhich are normally nonwrinkling in order to accelerate their drying rate and to improve and fully develop their wrinkle forming characteristics. This is brought about particularly by the introduction in said oils of organometallic compounds and metallic ions which serve to initiate polymerization and which tend largely to eliminate the necessity for the initial formation of polar bodies by means of oxidation of the oil. For example, linseed oil and soya bean oil are considered to be normally nonwrinkling oils; however, if these oils are subjected to blowing they are readily transformed into wrinkling oils and the reason forthis transformation is believed to be the formation of polar bodies due to the partial oxidation or the introduction of oxygen in the oil molecules.

It should be noted carefully thatthe selection of the metallic ion, as well as the corresponding organo radical is of considerable importance and will. lead to great variations in the results to be attained. It is reasonable to expect that most of the metals will react under the proper condi- 1 action in order to accomplish the correct attachment of the metallic ion to the olefinic bond.

It is important to note here the difference between the construction of an oil molecule treated in this manner and the ordinary drier composition generally used in the art to accelerate drying of oils. In this case the metallic ions are attached to one or more carbons at their initial points of unsaturation either by means of organometallic compound or other chemical reactions which will serve to orient the metallic ion to this position, while in ordinary driers the metallic ion is reacted with the acid group to form a 6-0-1! composition. The resulting difference in the polymerization is quite marked since the C-M linkage allows a much closer network of interreacting molecules than that experienced by any P lymerization caused by driers of the general type now employed in the art.

Of principal importance in the selection of an organo group is the formation of an organemetallic compound which will unite readily with the oil to allow the initial polymerization. For

the most part aliphatic groupings appear to be most satisfactory although in some cases aromatic and alicyclic radicals yield more desirable results.

Organometallic compounds of the type employed according to the present invention areintending to limit the present invention, there is given below a diagrammatic presentation of the manner in which a small amount of these compounds can initiate polymerization of the oil molecule. The oleic acid radical and a simple organometallic compound is used.

From this simple illustration it is interesting to picture the complexity involved when a triglyceride made up of acid radicals containing more than one unsaturated bond is treated with an organometallic compound,

As has been mentioned hereinbefore, it may be desirable in some cases to add the metallic ion to the olefin linkage by means other than through the use of the organometallic unit. The alkali metals, for instance, will add directly into the double bond and the resulting polymerization is similar to that pictured above.-

The fundamental principles of the, present invention are applicable to the treatment of other esters of drying oils besides the triglyceride formation. Typical of these are those obtained by the reaction of unsaturated fatty acids with monohydric alcohols and other polyhydric alcohols than trihydric. These substances possess potential drying properties which may be developed under proper conditions and which, with the aid of the polymerizing nucleus which results from the practice of the present invention will harden and produce suitable films.

Further, by way of illustration, and without thereby intending to limit the present invention, the following examplesare given:

Example I 100 grams of linseed oil are placed in a suitable containerprovided with a cover, a gas inlet for furnishing a blanket of inert gas over the surface of the oil, a suitable condenser for condensing 4 inflammable volatile matter, and a stirring device. Nitrogen gas is then introduced through the inlet at a slow but constant rate and 0.12 gram of CsCzHs in 20 grams oi! diethyl ether is added. The stirrer is started and the contents allowed to react at room temperature for approximately 4 hours. Theheat is then increased to approximately 50 C. for the removal of the ether and then to 200 C. at which temperature it is held for a period of about 4 hours until a rather viscous oil results. The nitrogen supply is shut of! approximately 1 hour prior to the completion 0! the cook.

i The resulting product is a viscous oil possessing a highly increased drying rate and wrinkle forming properties which when compounded with resin and driers as is customary in the art willproduce a coating composition which will yield a. well defined uniform wrinkle film on application and drying.

' Example II 50 grams of an esterifled mixture of linseed oiljfatty acids and ethylene glycol are placed in a container-such as described in Example I. 0.2 gram of CO(CH2-CH=CH2)2 in 20 grams of diethyl ether are then added to the container.

Nitrogen is introduced to provide an inert blanket over the mixture and the stirrer is started. The contents are allowed to react for approximately 2 hours at room temperature and the temperature is then increased to approximately 50C. for the removal of the ether and then to approximately 250 C. The mixture is maintained at this temperature for about 2 hours and 50 grams of the original ester is then added. At this point the temperature will rapidly drop, and it is then increased to 200 C. and kept at this level until the oil is quite viscous.

The product resulting from this treatment may be used in the usual manner in compounding wrinkle, coating compositions and will produce results not unlike those obtained with the prod uct ot.Example I.

' Example III 100 grams of soya bean are placed in a container such as described in Example I and 0.15 gram of Pb(C3H'i)2 added, and the mixture treated in the manner described in Example 1. After the removal or the ether, however, the temperature is increased to 300 C. and maintalned at that level for approximately 8 hours or until the oil reaches the desired degree of viscosity. The inert blanket of nitrogen is maintained throughout this treatment.

The product resulting from this treatment may be used in the same manner and will exhibit the same properties as the products resulting from the treatment of Examples I and II.

It will be understood that the foregoingexamples are illustrative of the application of the method of the present invention, and that it is not intended to have the present invention limited to or circumscribed by the particular details of procedure, materials, or apparatus therein set forth or described in view of the fact that the present invention is susceptible to modifications depending on individual preference and conditions without departing from the spirit of this disclosure and the scope of the appended claims.

I claim:

1. The method of making a wrinkling oil from an ester of non-wrinkling oil fatty acids which consists in heating said ester in an inert ambient atmosphere at a maximum temperature of 250 C. with allyl cobalt.

2. The method of making a wrinkling oil from untreated normally non-wrinkling oil which consists in heating said oil in an inert ambient atmosphere at a maximum temperature of 250". C. with allyl cobalt.

3. The method of making a wrinkling oil from an ester of non-wrinkling oil fatty acids which consists in adding a solution of 0.2 gram of allyl cobalt in approximately 20 grams of diethyl ether to 50 grams of said ester and allowing the mixture to remain at room temperature for approximately two hours while maintaining an inert ambient atmosphere; thereafter removing the ether by heating to approximately 50 C.; then heating to about 250 C. for approximately one hour; adding another 50 grams of said ester;

and heating the mixture to substantially 200 C. until the desired viscosity is obtained.

4. The method of making a wrinking oil from untreated normally non-wrinkling oil which consists in adding a solution of 0.2 gram of allyl cobalt in approximately 20 grams of diethyl ether to 50 grams of said oil and allowing the mixture to remain at room temperature for approximately two hours while maintaining an inert ambient atmosphere; thereafter removin the ether by heating to approximately 50 C.; then heating to about 250 C. for approximately one hour; adding another 50 grams of said 011; and heating the mixture to substantially 200 C. until the desired viscosity is obtained.

5. The method of making a wrinkling oil from an ester formed of linseed oil fatty acids and ethylene glycol which consists in adding a solution of 0.2 gram of allyl cobalt in approximately 20 grams of diethyl ether to 50 grams of said ester and allowing the mixture to remain at room temperature for approximately two hours while maintaining an inert ambient atmosphere; thereafter removing the ether by heating to approximately 50 0.; then heating to about 250 C. for approximately one hour; adding another 50 grams of said ester; and heating the mixture to substantially 200 c. until the desired viscosity is obtained.

GORDON M. WILLIAMS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,891,203 Ambros Dec. 13, 1932 2,024,103 Krvmbhaar Dec. 10, 1935 2,294,703 Waldie Sept. 1, 1942 2,298,270 Auer Oct. 13, 1942 2,298,271 Auer Oct. 13, 1942 2,298,915 Auer Oct.- 13, 1942 2,308,595 Drummond Jan. 19, 1943 

